Stabilizer mixture

ABSTRACT

The invention relates to mixtures, comprising
         (a) an oligomeric compound, comprising repeat units of the general formula (I) or acid-addition salts thereof       

     
       
         
         
             
             
         
       
         
         
           
             and/or 
             (b) a compound of the general formula (II) or acid-addition salts thereof 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             and 
             (c) at least one compound of the general formula (III) 
             and 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             (d) optionally further additives,
 
and also to the use of these mixtures for the stabilization of non-living organic materials with respect to exposure to light, oxygen, and/or heat. The invention further relates to non-living organic materials, comprising at least one of these mixtures, and to articles produced therefrom. The invention further relates to a process for the stabilization of non-living organic materials, with respect to exposure to light, oxygen, and/or heat.

This application is a continuation of U.S. application Ser. No. 12/675,037 filed Feb. 24, 2010, which is a National Stage of PCT/EP2008/060173 filed Aug. 1, 2008, both of which are incorporated herein by reference. This application also claims the benefit of EP 07115133.6 filed Aug. 28, 2007.

DESCRIPTION

The invention relates to mixtures, which comprise

-   -   (a) an oligomeric compound, comprising repeat units of the         general formula (I) or acid-addition salts thereof

-   -   in which     -   R¹ is H, C₁-C₃₀-alkyl, C₂-C₂₂-alkenyl, C₁-C₂₀-alkoxy,         cyanomethyl, 2-hydroxyethyl, formyl, C₂-C₆-alkanoyl, benzyl, or         a moiety of the formula —CR⁷═CH—CO—OR⁸,     -   R² is H, C₁-C₃₀-alkyl, or a mixture composed of C₁₄-C₂₈-alkyl         groups,     -   R³, R⁴, R⁵, and R⁶, independently of one another, are identical         or different C₁-C₃₀-alkyl,     -   R⁷ is H, C₁-C₈-alkyl, or a moiety of the formula CO—OR⁸,     -   R⁸ is C₁-C₁₈-alkyl, C₃-C₁₅-cycloakyl, C₇-C₁₈-aralkyl, phenyl or         tolyl,     -   and/or     -   (b) a compound of the general formula (II) or acid-addition         salts thereof

-   -   in which     -   n is 1 or 2,     -   R⁹ is H or C₁-C₄-alkyl,     -   R¹⁰, R¹¹, R¹², and R¹³, independently of one another, are         identical or different C₁-C₄-alkyl, or R¹⁰ and R¹¹ or R¹² and         R¹³ together are a tetramethylene group or pentamethylene group,     -   R¹⁴ is H, C₁-C₃₀-alkyl, or C₂-C₂₂-alkenyl, or unsubstituted or         C₁-C₄-alkyl-, halogen-, C₁-C₄-alkoxy-, methylenedioxy-,         ethylenedioxy-, and/or di-C₁-C₄-alkylamino-substituted         C₇-C₁₂-phenylalkyl, C₁-C₂₂-alkanoyl, C₂-C₃-cyanoalkyl,         C₁-C₂₂-hydroxyalkyl or C₂-C₂₂-aminoalkyl,     -   R¹⁶ is H or C₁-C₃₀-alkyl,     -   and     -   if n=1     -   R¹⁵ is H, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₃-C₁₂-cycloalkyl or         bicycloalkyl, or cyano-, hydroxyl-, or         carbo-C₁-C₄-alkoxy-substituted C₂-C₂₂-alkyl, or ether-oxygen-,         nitrogen-, or sulfur-interrupted C₄-C₂₂-alkyl, or unsubstituted         or C₁-C₄-alkyl-, halogen-, C₁-C₄-alkoxy-, methylenedioxy-,         ethylenedioxy-, or di-C₁-C₄-alkylamino-substituted         C₇-C₂₂-phenyl- or diphenylalkyl, or unsubstituted or         C₁-C₄-alkyl- or carbo-C₁-C₄-alkoxy-substituted phenyl, or a         moiety of the general formula (IV)

-   -   -   or C₁-C₂₂-alkyl comprising heterocyclic moieties, or

    -   if n=2—

    -   R¹⁵ is C₂-C₂₂-alkylene, C₅-C₂₂-cycloalkylene,         C₈-C₁₄-phenylalkylene, or phenylene, or ether-oxygen-,         nitrogen-, or sulfur-interrupted C₄-C₃₀-alkylene, or         C₄-C₃₀-alkylene interrupted by 5- or 6-membered heterocyclic         moieties,

    -   and

    -   (c) at least one compound of the general formula (III)

-   -   in which     -   R¹⁷ is C₁-C₂₀-alkyl or aryl,     -   and     -   optionally further additives.

The present invention moreover describes processes for the stabilization of non-living organic materials, in particular plastics, with respect to exposure to light, oxygen, and/or heat, using this mixture. The invention further relates to articles which are produced from non-living organic materials thus stabilized.

Further embodiments of the present invention are given in the claims, in the description, and in the examples. The abovementioned features, and the features that will be explained below, of the inventive subject matter can, of course, be used not only in the respective combination specifically stated but also in other combinations, without exceeding the scope of the invention. Preference and, respectively, a high level of preference are also particularly given to those embodiments of the present invention in which all of the features of the inventive subject matter have the preferred or, respectively, the very preferred definitions.

Non-living organic materials, in particular plastics, are known to undergo very rapid irreversible damage especially through exposure to light, oxygen, and/or heat. This irreversible damage usually takes the form of yellowing, discoloration, cracking, or embrittlement of the material. The use of light stabilizers and of other stabilizers is therefore intended to provide satisfactory protection from irreversible damage to non-living organic material due to light, oxygen, and/or heat.

Derivates of 2,2,6,6-tetraalkylpiperidine, called HALS (Hindered Amine Light Stabilizers) have now been used commercially for about three decades in the form of light stabilizers and other stabilizers, in particular for plastics and coatings.

WO 2004/046234 A2 discloses stabilizer mixtures which comprise a UV absorber and at least one further component, selected from a group of five classes of compound. UV absorbers mentioned are inter alia benzoates, and sterically hindered amines can also be one of the further components. No combination composed of hydroxybenzoates with HALS compounds is disclosed.

JP 2003253083 describes a propylene-ethylene block copolymer which comprises from 0.03 to 3% of a mixture composed of alkyl benzoate and HALS.

JP 10195258 discloses agriculture foils composed of polyolefins, stabilized with HALS and with benzoates.

U.S. Pat. No. 6,897,250 B1 describes automobile parts composed of thermoplastic elastomers, which comprise from 0.001 to 10% of alkyl benzoates and from 0.1 to 0.5% of HALS.

Although these compounds and mixtures have been proven outstandingly successful in previous commercial use, there is nevertheless scope for improvements, particularly relating to resistance to light with high UV content.

It was therefore an object of the present invention to provide mixtures which provide improved stabilization of non-living organic material with respect to light with high UV content and/or high light intensity. A further object of the invention was to provide mixtures which offer a high degree of stabilization and which are based on starting materials that are easy to obtain. A further subobject of the present invention was to provide mixtures which provide improved stability of non-living organic material with respect to oxygen or heat.

The mixtures described in the introduction have accordingly been found.

For the purposes of this invention, expressions of the type C_(a)—C_(b) indicate chemical compounds or substituents having a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, inclusive of a and b, and a is at least 1, and b is always greater than a. Further specification of the chemical compounds or of the substituents is achieved via expressions of the type C_(a)—C_(b)-V. V here is a class of chemical compound or class of substituent, for example alkyl compounds or alkyl substituents.

Halogen is fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine, particularly preferably fluorine or chlorine.

The individual definitions of various collective terms given are as follows:

C₁-C₃₀-alkyl: straight-chain or branched hydrocarbon moieties having up to 30 carbon atoms, for example C₁-C₁₈-alkyl, C₁-C₁₀-alkyl, or C₁₁-C₂₀-alkyl, preferably C₁-C₁₀-Alkyl, for example C₁-C₆-alkyl, C₁-C₄-alkyl, C₁-C₃-alkyl, such as methyl, ethyl, n-propyl, isopropyl, or C₄-C₆-alkyl, n-butyl, sec-butyl, 1,1-dimethylethyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1,1,2-trimethyl-propyl, 1,2,2-tri-methylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C₇-C₁₀-alkyl, such as heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl (e.g. 2-propylheptyl), and also their isomers. C₂-C₂₂-alkenyl: unsaturated, straight-chain, or branched hydrocarbon moieties having from 2 to 22 carbon atoms and having at least one double bond, preferably having one double bond, in any desired position, for example C₂-C₁₀-alkenyl or C₁₁-C₂₂-alkenyl, preferably C₂-C₁₀-alkenyl such as C₂-C₄-Alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, or C₅-C₆-alkenyl, such as 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-di-methyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-di-methyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-di-methyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-di-methyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl or 1-ethyl-2-methyl-2-propenyl, or else C₇-C₁₀-alkenyl, such as the isomers of heptenyl, octenyl, nonenyl or decenyl. C₃-C₁₅-cycloalkyl: monocyclic, saturated hydrocarbon groups having from 3 up to 15 carbon ring members, preferably C₃-C₈-Cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl or else a saturated or unsaturated cyclic system, e.g. norbornyl or norbornenyl. C₅-C₆-cycloalkyl is particularly preferred. C₁-C₂₂-alkanoyl: a straight-chain or branched alkyl group having from 1 to 22 carbon atoms (as mentioned above) which have linkage by way of a carbonyl group (—CO—), for example C₁-C₁₁-alkanoyl or C₁₂-C₂₂-alkanoyl, preferably C₁-C₁₁-alkanoyl, such as C₁-C₆-alkanoyl, such as formyl, acetyl, n- or isopropionyl, n-, iso-, sec- or tert-butanoyl, n-, iso-, sec- or tert-pentanoyl, hexanoyl, or C₉-C₁₂-alkanoyl, such as n- or isononanoyl, or n-dodecanoyl.

Aryl: a mono- to trinuclear aromatic ring system comprising from 6 to 14 carbon ring members, e.g. phenyl, hydroxyphenyl, naphthyl, or anthracenyl, preferably a mono- to binuclear, particular preferably a mononuclear, aromatic ring system.

Substituted aryl moieties: aryl moieties which can have substitution at any desired position, but not more than 5 times, preferably not more than 4 times, particularly preferably not more than 3 times, and very particularly preferably twice or once, by C₁-C₂₀-alkyl or by hydroxy.

Aralkyl: aryl-substituted alkyl moieties. Examples are naphthylmethyl, diphenylmethyl or methylbenzyl, in particular 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenyl-propyl, 3-phenylpropyl, 2-phenyl-prop-2-yl, 4-phenylbutyl, 2,2-dimethyl-2-phenylethyl, 5-phenylamyl, 10-phenyldecyl, 12-phenyldodecyl, or especially benzyl. Preferably C₇-C₁₈-aralkyl: aryl-substituted alkyl moieties with 7 to 18 hydrocarbon atoms. Tolyl moieties that can be used are ortho-, meta-, and especially p-tolyl.

Heterocyclic moieties: five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered, ring systems having oxygen atoms, nitrogen atoms, and/or sulfur atoms and, if appropriate, having a plurality of rings, examples being furyl, thiophenyl, pyrryl, pyridyl, imidazoyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl, or tert-butylthiophenyl.

C₁-C₂₀-alkoxy is defined as a straight-chain or branched alkyl group having from 1 to 20 carbons atoms (as mentioned above) linked by way of an oxygen atom (—O—), for example C₁-C₁₀-alkoxy, such as n-hexoxy, isohexoxy, n-octoxy, 2-ethylhexoxy and isooctoxy, and also methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-nonoxy, n-decoxy, or C₁₁-C₂₀-Alkoxy such as n-undecoxy and n-dodecoxy, preferably C₁-C₁₀-alkyloxy, particularly preferably C₁-C₃-alkoxy such as methoxy, ethoxy, propoxy.

C₁-C₂₂-alkylene: straight-chain or branched hydrocarbon moieties having from 1 to 22 carbon atoms, for example C₂-C₁₀-alkylene or C₁₁-C₂₂-alkylene, preferably C₂-C₁₀-alkylene, in particular methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene.

C₅-C₂₂-cycloalkylene: straight-chain or branched hydrocarbon moieties having from 5 to 22 carbon atoms, where one alkylene moiety has interruption by a cycloalkyl group, i.e. two hydrogens of the cycloalkyl group have been replaced by alkylene moieties.

C₈-C₁₄-phenylalkylene: straight-chain or branched hydrocarbon moieties having from 8 to 14 carbon atoms, where the alkylene chain has interruption by a phenylene group.

C₁-C₂₂-hydroxyalkyl: a C₁-C₂₂-alkyl moiety substituted at any desired position by a hydroxy group.

C₁-C₂₂-aminoalkyl: a C₁-C₂₂-alkyl moiety substituted at any desired position by an amino group.

Each of the individual substituents R¹ to R¹⁷ listed can have interruption at any desired position by one or more heteroatoms, where the number of these heteroatoms is not more than 10, preferably not more than 8, very particularly preferably not more than 5, and in particular not more than 3 and/or each of the substituents R¹ to R¹⁷ can have substitution at any desired position, but not more than five times, preferably not more than four times, and particularly preferably not more than three times by C₁-C₃₀-alkyl, C₁-C₂₀-alkoxy, aryl, heterocyclic moieties, heteroatoms, or halogen, and these likewise can have substitution at most twice, preferably at most once by the groups mentioned or by substituted aryl moieties.

The definition of the classes of compound mentioned in this group: C₁-C₃₀-alkyl, C₁-C₂₀-alkoxy, aryl and heterocyclic moieties, is as mentioned above.

Heteroatoms are preferably oxygen, nitrogen, sulfur, or phosphorus.

Acid-addition salts are the salts of the respective compounds with mineral acids, for example HCl, or with organic acids, for example acetic acid.

Component (a) in the inventive mixtures can comprise one or more different oligomeric compounds, comprising repeat units of the general formula (I), or their acid-addition salts.

Components (b) in the inventive mixtures can moreover comprise one or more different compounds of the general formula (II) or their acid-addition salts.

Components (c) in the inventive mixtures can moreover comprise one or more different compounds of the general formula (III), and component (d) in the inventive mixtures can optionally comprise one or more additives.

The average molecular weight of the oligomeric compounds of the component (a) is generally from 1000 to 50 000, preferably from 1500 to 10 000, and in particular from 3000 to 5000. The molecular weights stated are number-average molecular weights. The average number of repeat units in the oligomeric compounds is from 3 to 100, preferably from 4 to 30, in particular from 5 to 10.

The moiety R¹ is preferably H, C₁-C₆-alkyl, formyl, acyl, C₁-C₆-alkoxy, benzyl, or a moiety of the formula —CH═CH—CO—R′, where R′ is C₁-C₆-alkyl, in particular methyl or ethyl. R¹ is particularly preferably H, methyl, or C₁-C₆-alkoxy, in particular H.

The moiety R² is preferably C₁₂-C₃₀-alkyl. The moiety R² can moreover be a mixture composed of C₁₄-C₂₈-alkyl groups, preferably C₁₆-C₂₄-alkyl, in particular C₁₈-C₂₂-alkyl. R² is preferably linear alkyl groups.

The presence of a mixture of alkyl groups for R² is to be understood to mean that, taking a statistical average over the entire number of all of the alkyl groups present, two particular alkyl groups which do not differ by more than two carbon atoms respectively make up at least 30%, preferably respectively at least 40%, of this mixture. In particular, these are mixtures of three particular alkyl groups, for example octadecyl, eicosyl, and docosyl, where two of these groups which differ by 2 carbon atoms make up more than 40% of the mixture and the third group makes up from 3 to 18% of the mixture; the mixture here can comprise very small amounts of further alkyl groups having somewhat fewer than 18 or somewhat more than 22 carbon atoms, these amounts usually being less than 2%.

The moieties R³, R⁴, R⁵, and R⁶ are preferably C₁-C₄-alkyl, particularly preferably methyl, and it is particularly preferable that each of the moieties R³, R⁴, R⁵, and R⁶ is methyl.

Particular preference is given to an oligomeric compound of component (a) which is an oligomeric compound having the repeat unit (la)

and having a number-average molar mass of from 3000 to 4000 g/mol.

A compound of this type is obtainable as Uvinul® 5050 H from BASF Aktiengesellschaft, Ludwigshafen, Germany.

Particularly preferred oligomeric compounds of components (a) are those in which a maximum number, in particular all, of the substituents, symbols, and indices assume their preferred or particularly preferred definition.

The oligomeric compounds of component (a) can, if the compounds are not commercially available, be prepared by the methods stated in WO 94/12544.

Among the compounds of the general formula (II) of component (b), preference is given to those in which the definitions of the symbols and indices are as follows:

R¹⁴ is preferably H, C₁-C₄-alkyl, formyl, acyl, or benzyl, particularly preferably H, methyl, formyl, acyl, or benzyl, in particular H.

R¹⁰, R¹¹, R¹², and R¹³ are preferably C₁-C₄-alkyl, particularly preferably methyl, and it is particularly preferable that all of the moieties R¹⁰, R¹¹, R¹², and R¹³ are methyl.

R¹⁶ is preferably H.

n is preferably 2.

If n=2, R¹⁵ is preferably C₂-C₂₂-alkylene, particularly preferably C₄-C₁₀-alkylene, very particularly preferably C₆-C₈-alkylene, in particular C₆-alkylene.

Particular preference is given, as compound of the general formula (II) of component (b), to the compound (IIa)

which is commercially obtainable as Uvinul® 4050 H from BASF Aktiengesellschaft, Ludwigshafen, Germany.

Particularly preferred compounds of the general formula (II) of component (b) are those in which a maximum number, in particular all, of the substituents, symbols, and indices assume their preferred or particularly preferred definition.

Compounds of the general formula (II), in particular components of the formula (IIa), can, if they are not commercially available, be prepared by the methods described in EP-A 0 316 582 and GB 2311292.

Among the compounds of the general formula (III) of component (c), preference is given to those in which the definitions of the symbols and indices are as follows:

R¹⁷ is preferably C₁₀-C₂₀-alkyl or a substituted aryl moiety, very preferably C₁₄-C₁₈-alkyl or a substituted phenyl moiety, in particular a C₁₋₆-alkyl moiety (C₁₆H₃₃) or disubstituted phenyl moiety. R¹⁷ is very particularly preferably either a linear C₁₋₆-alkyl moiety or a 2,4-di-tert-butylphenyl moiety.

Compounds of the general formula (III) can, if they are not commercially available, be prepared by familiar methods known to the person skilled in the art, as described by way of example in the specifications U.S. Pat. No. 4,128,726 and EP 139919.

The ratio by weight of components (a) and (b) in the inventive mixtures is generally, if the two components are present, from 5:1 to 1:5, preferably from 2:1 to 1:2, particularly preferably from 1.2:1 to 1:1.2, and particular preference is given to a mixture in which the ratio by weight is about 1:1.

If no component (b) is present, the ratio by weight of components (a) and (c) in the inventive mixtures is generally from 10:1 to 1:2, preferably from 5:1 to 1:1, particularly preferably from 2:1 to 1:1, and particular preference is given to a mixture in which the ratio by weight is about 2:1.

If no component (a) is present, the ratio by weight of components (b) and (c) in the inventive mixtures is generally from 10:1 to 1:2, preferably from 5:1 to 1:1, particularly preferably from 2:1 to 1:1, and particular preference is given to a mixture in which the ratio by weight is about 2:1.

If component (a) and component (b) are present, the ratio by weight of the entirety of components (a) and (b) to component (c) in the inventive mixtures is generally from 10:1 to 1:2, preferably from 5:1 to 1:1, particularly preferably from 2:1 to 1:1, and particular preference is given to a mixture in which the ratio by weight is about 2:1.

The inventive mixtures can be prepared by familiar processes known to the person skilled in the art.

A possible preferred method adds component (c) to a melt of component (a) and/or (b), homogenizes the mixture, converts it to the desired shape, for example pastilles, and allows it to cool.

However, it is also possible to mix solutions of components (c) and (a) and/or (b), and then to remove the solvent(s).

Another possibility is to combine the products which, if appropriate, have been previously ground. The mixture can also, if appropriate, be converted to a suitable form, for example via pelletization, after the mixing process.

The invention therefore also provides an appropriate process for the preparation of the inventive mixtures.

The following combinations of compounds of components (c) and (a), and/or (b) are particularly preferred:

the combination of the compounds (IIIa) or (IIIb) with (Ia), (IIIa) or (IIIb) with (IIa), and also of a mixture composed of (Ia) and (IIb) with (IIIa) or (IIIb)

Particular preference is given to the combination of the compound (Ia) with the compound (IIIa), and to the combination of the compounds (Ia) and (IIIb).

The inventive mixtures have excellent suitability for use as stabilizers for the stabilization of non-living organic material with respect to exposure to light, oxygen, and heat. The inventive mixtures are added to the non-living organic materials to be stabilized, the concentration added generally being sufficient to achieve the desired stabilizing action. The concentration added of the inventive mixtures prior to, during, or after the production of the non-living organic material is preferably from 0.01 to 5% by weight, with preference from 0.02 to 1% by weight, based on the non-living organic material.

The form in which the inventive mixture is added to the non-living organic material to be protected can be that of a prefabricated mixture of components (a) and/or (b), and (c), but it is equally possible to add components (a) and/or (b), and (c) separately to the material to be protected, in which case the mixture is not produced until it is within the material to be protected. Separate addition of components (a) and/or (b), and (c) can take place simultaneously or non-simultaneously, and the sequence here is generally not important.

Examples of non-living organic material are cosmetic preparations, such as ointments and lotions, pharmaceutical formulations, such as pills and suppositories, photographic recording material, such as photographic emulsions, or precursors of plastics and coatings, but in particular plastic and coatings themselves. Articles can be produced from non-living organic material.

The invention also provides non-living organic material stabilized with respect to exposure to light, oxygen, and heat, in particular plastics and coatings, where the material comprises the inventive mixtures, preferably at the concentrations stated above.

Any of the known apparatuses and methods for mixing to incorporate stabilizing compositions or other additives into polymers can be used for the mixing of the inventive mixture, especially with plastics.

The inventive mixture optionally additionally comprises, as component (d), or the non-living organic material to be stabilized by the mixture optionally additionally comprises, at least one further light stabilizer and/or further (co)stabilizers. Examples of suitable light stabilizers and further (co)stabilizers are those selected from the groups a) to s):

a) 4,4-diarylbutadienes, b) cinnamic esters, c) benzotriazoles, d) hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides, g) 2-phenyl-1,3,5-triazines; h) antioxidants, i) nickel compounds, j) sterically hindered amines which differ from the compounds of the general formulae (I) and (II) k) metal deactivators, l) phosphites and phosphonites, m) hydroxylamines, n) nitrones, o) amine oxides, p) benzofuranones and indolinones, q) thiosynergists, r) peroxide-destroying compounds, and s) basic costabilizers.

The group a) of the 4,4-diarylbutadienes includes, for example, compounds of the formula (aa)

The compounds are known from EP-A-916 335. The substituents R¹⁹ and R²⁰ are, independently of one another, identical or different, preferably being C₁-C₈-alkyl and C₅-C₈-cycloalkyl.

The group b) of the cinnamic esters includes, for example, 2-isoamyl 4-methoxy-cinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl α-(methoxycarbonyl)cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, and methyl α-(methoxycarbonyl)-p-methoxycinnamate.

The group c) of the benzotriazoles includes, for example, 2-(2′-hydroxyphenyl)benzo-triazoles, such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyl)benzotriazole, 2-(5′-(tert-butyl)-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di(tert-butyl)-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(3′-(sec-butyl)-5′-(tert-butyl)-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di(tert-amyl)-2′-hydroxyphenyl)-benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-(tert-butyl)-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzo-triazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzo-triazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-(tert-butyl)-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and 2-(3′-(tert-butyl)-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl)benzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetra-methylbutyl)-6-(benzotriazol-2-yl)phenol], the product of esterification of 2-[3′-(tert-butyl)-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300, [R—CH₂CH₂—COO(CH₂)₃]₂, where R=3′-(tert-butyl)-4′-hydroxy-5′-(2H-benzotriazol-2-yl)phenyl, and mixtures thereof.

The group d) of the hydroxybenzophenones includes, for example, 2-hydroxybenzo-phenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzo-phenone, 2-hydroxy-4-(2-ethylhexyloxy)benzophenone, 2-hydroxy-4-(n-octyloxy)benzo-phenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-3-carboxybenzo-phenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disulfonic acid and its sodium salt.

The group e) of the diphenylcyanoacrylates includes, for example, ethyl 2-cyano-3,3-diphenylacrylate, which, for example, is obtainable commercially as Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, which, for example, is obtainable commercially as Uvinul® 3039 from BASF AG, Ludwigshafen, and 1,3-bis[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis{[(2′-cyano-3′,3′-diphenyl-acryloyl)oxy]methyl}propane, which, for example, is obtainable commercially as Uvinul® 3030 from BASF AG, Ludwigshafen.

The group f) of the oxamides includes, for example, 4,4′-dioctyloxyoxanilide, 2,2′-di-ethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di(tert-but)oxanilide, 2,2′-didodecyloxy-5,5′-di(tert-but)oxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-(tert-butyl)-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di(tert-but)oxanilide, and also mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

The group g) of the 2-phenyl-1,3,5-triazines includes, for example, 2-(2-hydroxy-phenyl)-1,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-di-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-di-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-(butyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-(octyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-(dodecyloxy)propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

The group h) of the antioxidants comprises, for example:

alkylated monophenols, for example 2,6-di(tert-butyl)-4-methylphenol, 2-(tert-butyl)-4,6-dimethylphenol, 2,6-di(tert-butyl)-4-ethylphenol, 2,6-di(tert-butyl)-4-(n-butyl)phenol, 2,6-di(tert-butyl)-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methyl-cyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclo-hexylphenol, 2,6-di(tert-butyl)-4-methoxymethylphenol, unbranched nonylphenols or nonylphenols which are branched in the side chain, such as, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol, 2,4-dimethyl-6-(1-methyl-heptadec-1-yl)phenol, 2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-(tert-butyl)phenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol and 2,6-didodecylthiomethyl-4-nonylphenol.

Hydroquinones and alkylated hydroquinones, for example 2,6-di(tert-butyl)-4-methoxyphenol, 2,5-di(tert-butyl)hydroquinone, 2,5-di(tert-amyl)hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di(tert-butyl)hydroquinone, 2,5-di(tert-butyl)-4-hydroxyanisole, 3,5-di(tert-butyl)-4-hydroxyanisole, 3,5-di(tert-butyl)-4-hydroxyphenyl stearate and bis(3,5-di(tert-butyl)-4-hydroxyphenyl) adipate.

Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-(tert-butyl)-4-methyl-phenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-(tert-butyl)-3-methylphenol), 4,4′-thio-bis(6-(tert-butyl)-2-methylphenol), 4,4′-thiobis(3,6-di(sec-amyl)phenol) and 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

Alkylidenebisphenols, for example 2,2′-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2′-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di(tert-butyl)phenol), 2,2′-ethylidenebis(4,6-di(tert-butyl)phenol), 2,2′-ethylidenebis(6-(tert-butyl)-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di(tert-butyl)phenol), 4,4′-methylenebis(6-(tert-butyl)-2-methylphenol), 1,1-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-(tert-butyl)-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-(tert-butyl)-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)-3-(n-dodecylmercapto)butane, ethylene glycol bis[3,3-bis(3-(tert-butyl)-4-hydroxyphenyl)butyrate], bis(3-(tert-butyl)-4-hydroxy-5-methyl phenyl)dicyclopentadiene, bis[2-(3′-(tert-butyl)-2-hydroxy-5-methylbenzyl)-6-(tert-butyl)-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di(tert-butyl)-4-hydroxyphenyl)propane, 2,2-bis(5-(tert-butyl)-4-hydroxy-2-methylphenyl)-4-(n-dodecylmercapto)butane and 1,1,5,5-tetra(5-(tert-butyl)-4-hydroxy-2-methylphenyl)pentane.

Benzyl compounds, for example 3,5,3′,5′-tetra(tert-butyl)-4,4′-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di(tert-butyl)benzylmercaptoacetate, tris(3,5-di(tert-butyl)-4-hydroxybenzyl)amine, 1,3,5-tri(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di(3,5-di(tert-butyl)-4-hydroxybenzyl) sulfide, isooctyl 3,5-di(tert-butyl)-4-hydroxybenzylmercaptoacetate, bis(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di(tert-butyl)-4-hydroxybenzyl dioctadecyl phosphate and 3,5-di(tert-butyl)-4-hydroxybenzyl monoethyl phosphate, calcium salt. Hydroxybenzylated malonates, for example dioctadecyl 2,2-bis(3,5-di(tert-butyl)-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-(tert-butyl)-4-hydroxy-5-methyl-benzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di(tert-butyl)-4-hydroxy-benzyl)malonate and bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate.

Hydroxybenzyl aromatic compounds, for example 1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di(tert-butyl)-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tris(3,5-di(tert-butyl)-4-hydroxybenzyl)phenol.

Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di(tert-butyl)-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di(tert-butyl)-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di(tert-butyl)-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di(tert-butyl)-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di(tert-butyl)-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-(tert-butyl)-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di(tert-butyl)-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Benzylphosphonates, for example dimethyl 2,5-di(tert-butyl)-4-hydroxy-benzylphosphonate, diethyl 3,5-di(tert-butyl)-4-hydroxybenzylphosphonate ((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methylphosphonic acid diethyl ester), dioctadecyl 3,5-di(tert-butyl)-4-hydroxybenzylphosphonate, dioctadecyl 5-(tert-butyl)-4-hydroxy-3-methylbenzylphosphonate and calcium salt of 3,5-di(tert-butyl)-4-hydroxybenzylphosphonic acid monoethyl ester.

Acylaminophenols, for example lauric acid 4-hydroxyanilide, stearic acid 4-hydroxyanilide, 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine and octyl N-(3,5-di(tert-butyl)-4-hydroxyphenyl)carbamate.

Esters of β-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as, e.g., with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(5-(tert-butyl)-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, such as, e.g., with methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as, e.g., with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Esters of 3,5-di(tert-butyl)-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as, e.g., with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapenta-decanol, trimethylhexanediol, trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

Amides of β-(3,5-di(tert-butyl)-4-hydroxyphenyl)propionic acid, such as, e.g., N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hydrazide and N,N′-bis[2-(3-[3,5-di(tert-butyl)-4-hydroxy-phenyl]propionyloxy)ethyl]oxamide (e.g. Naugard®XL-1 from Uniroyal).

Ascorbic Acid (Vitamin C)

Aminic antioxidants, such as N,N′-diisopropyl-p-phenylenediamine, N,N′-di(sec-butyl)-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylene-diamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-tolylsulfamoyl)-diphenylamine, N,N′-dimethyl-N,N′-di(sec-butyl)-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-(tert-octyl)phenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenyl-amine, e.g. p,p′-di(tert-octyl)diphenylamine, 4-(n-butylamino)phenol, 4-butyrylamino-phenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis(4-methoxyphenyl)amine, 2,6-di(tert-butyl)-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl-amino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixture of mono- and dialkylated tert-butyldiphenyl-amines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol, the dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol [CAS number 65447-77-0] (for example Tinuvin® 622 from Ciba Specialty Chemicals Inc.) and the polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one and epichlorohydrin [CAS No.: 202483-55-4] (for example Hostavin® N 30 from Clariant.).

The group i) of the nickel compounds includes, for example, nickel complexes of 2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, if appropriate with additional ligands, such as n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonates, e.g. the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if appropriate with additional ligands.

The group j) of the sterically hindered amines includes, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) (n-butyl)(3,5-di(tert-butyl)-4-hydroxybenzyl)malonate, bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl)malonate condensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-(tert-octylamino)-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(n-butyl)-2-(2-hydroxy-3,5-di(tert-butyl)benzyl)malonate, 3-(n-octyl)-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-bis(4-n-butyl-amino-2,2,6,6-tetramethylpiiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, condensation product of 2-chloro-4,6-di(4-(n-butyl)amino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine, and also 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorhydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine, poly[methylpropyl-3-oxo-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine and a hydrocarbon moiety of tert-amyl alcohol, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) glutarate, 2,4-bis{N[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2hydroxyethylamino)-s-triazine, hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidyl)-1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaazacyclopenta[def]fluorene-4,8-dione (z. B. Uvinul® 4049 from BASF AG, Ludwigshafen), poly[[6[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] [CAS No. 71878-19-8], 1,3,5-triazine-2,4,6-triamine, N,N′″-[1,2-ethanediylbis[[4,6-bis-[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)- (CAS No. 106990-43-6) (e.g. Chimassorb 119 from Ciba Specialty Chemicals, Inc.).

The group k) of the metal deactivators includes, for example, N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di(tert-butyl)-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, the bis(benzylidene) derivative of oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic bisphenylhydrazide, N,N′-diacetyladipic acid dihydrazide, N,N′-bis(salicyloyl)-oxalic acid dihydrazide or N,N′-bis(salicyloyl)thiopropionic dihydrazide.

The group l) of the phosphites and phosphonites includes, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di(tert-butyl)phenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di(tert-butyl)phenyl)pentaerythritol diphosphite, bis(2,6-di(tert-butyl)-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di(tert-butyl)-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di(tert-butyl)phenyl) 4,4′-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosphepin, 6-fluoro-2,4,8,10-tetra(tert-butyl)-12-methyldibenzo[d,g][1,3,2]dioxaphosphocin, bis(2,4-di(tert-butyl)-6-methylphenyl) methyl phosphite, bis(2,4-di(tert-butyl)-6-methylphenyl)ethyl phosphite, 2,2′,2″-nitrilo[triethyl-tris(3,3′,5,5′-tetra(tert-butyl)-1,1′-biphenyl-2,2′-diyl) phosphite] and 2-ethylhexyl (3,3′,5,5′-tetra(tert-butyl)-1,1′-biphenyl-2,2′-diyl) phosphite.

The group m) of the hydroxylamines includes, for example, N,N-dibenzylhydroxyl-amine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilauryl-hydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine and N,N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

The group n) of the nitrones includes, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, N-methyl-α-heptadecylnitrone and nitrones derived from N,N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.

The group o) of the amine oxides includes, for example, amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide.

The group p) of the benzofuranones and indolinones includes, for example, those disclosed in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052 or 5,252,643, in DE-A-4316611, in DE-A-4316622, in DE-A-4316876, in EP-A-0589839 or in EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di(tert-butyl)benzofuran-2-one, 5,7-di(tert-butyl)-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di(tert-butyl)-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di(tert-butyl)-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di(tert-butyl)benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one, Irganox® HP-136 from Ciba Specialty Chemicals and 3-(2,3-dimethylphenyl)-5,7-di(tert-butyl)benzofuran-2-one.

The group q) of the thiosynergists includes, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

The group r) of the peroxide-destroying compounds includes, for example, esters of β-thiodipropionic acid, e.g. the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide or pentaerythritol tetrakis(β-dodecylmercapto-propionate).

The group s) of the basic costabilizers includes, for example, melamine, polyvinyl-pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, the alkali metal and alkaline earth metal salts of higher fatty acids, e.g. calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

The inventive mixture can moreover comprise, as component (d), or the platic can comprise, other additives. Suitable additives of group t) which can be used are the conventional additives such as pigments, dyes, nucleating agents, fillers or reinforcing agents, antifogging agents, biocides, and antistatic agents.

Suitable pigments are inorganic pigments, for example the three crystalline forms of titanium dioxide: rutile, anatase, or brookite, or ultramarine blue, iron oxides, bismuth vanadates, or carbon black, or else the class of organic pigments, for example compounds from the class of the phthalocyanines, perylenes, azo compounds, isoindolines, quinophthalones, diketopyrrolopyrroles, quinacridones, dioxazines, and indanthrones.

Dyes are any of the colorants which in the plastic used undergo complete dissociation or are present with molecular dispersion and thus can be used to provide highly transparent, non-scattering coloration of polymers. Dyes are also considered to include organic compounds which fluoresce in the visible portion of the electromagnetic spectrum, examples being fluorescent dyes.

Suitable nucleating agents comprise, for example, inorganic substances such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates, or sulfates, preferably of alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids, and also their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, or sodium benzoate; polymeric compounds, such as ionic copolymers (“ionomers”).

Suitable fillers or reinforcing materials comprise, for example, calcium carbonate, silicates, talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour, and flours or fibers of other natural products, and synthetic fibers. Other examples of fibrous or pulverant fillers that may be used are carbon fibers or glass fibers in the form of glass textiles, glass mats, or glass silk rovings, chopped glass, or glass beads, and also Wollastonite. The form in which glass fibers are incorporated can either be that of short glass fibers or else that of continuous-filament fibers (rovings).

Examples of suitable antistatic agents are amine derivatives, such as N,N-bis(hydroxyalkyl)alkylamines or -alkyleneamines, polyethylene glycol esters, polyethylene glycol ethers, ethoxylated carboxylic esters, ethoxylated carboxamides, and glycerol mono- and distearates, and also their mixtures.

Examples which may be mentioned of plastics which can be stabilized by the inventive mixtures are:

thermoplastic elastomers; polymers of mono- and diolefins, for example low- and high-density polyethylene, polypropylene, linear poly-1-butene, polyisoprene, polybutadiene, and also copolymers of mono- or diolefins, or a mixture of the polymers mentioned; copolymers of mono- or diolefins with other vinyl monomers, for example ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers, or ethylene-acrylic acid copolymers; polystyrene, and also copolymers of styrene or α-methylstyrene with dienes and/or with acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methacrylate, acrylonitrile-butadiene-styrene (ABS), or methyl methacrylate-butadiene-styrene (MBS); Halogen-comprising polymers, for example polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, and also their copolymers; polymers which derive from α,β-unsaturated acids and from their derivatives, for example polyacrylates, polymethacrylates, polyacrylamides, and polyacrylonitriles; polymers which derive from unsaturated alcohols and amines or from their acrylic derivatives or acetals, for example polyvinyl alcohol and polyvinyl acetate; polyurethanes, polyamides, polyureas, polyesters, polycarbonates, polysulfones, polyether sulfones, and polyether ketones.

It is also possible to use the inventive mixtures to stabilize coatings, for example industrial coatings. Among these, particular emphasis should be given to baking enamel systems, and among these in turn to vehicle paint systems, preferably two-layer paint systems. An example of another application sector is paints for exterior paintwork on buildings, or on other structures, or on industrial apparatuses.

The inventive mixtures can be added in solid or dissolved form to the coating. Their good solubility in coating systems is particularly advantageous here.

The inventive mixtures are preferably used for the stabilization of thermoplastic elastomers, for example polyolefin-based thermoplastic elastomers. The inventive mixtures are in particular used in the stabilization of molding compositions composed of the materials mentioned.

Another preferred field of use is the stabilization of low- and high-density polyethylene, and also of polypropylene and polyamide, and by way of example also of fibers composed thereof.

The inventive mixtures exhibit improved stabilization of non-living organic material with respect to light with high UV content and/or with high light intensity. The inventive mixtures are moreover based on starting materials that are easy to obtain. With the aid of the inventive mixtures it is possible to provide efficient protection of non-living organic material with respect to oxygen or heat.

The above embodiments of the inventive process, and the examples below, provide examples of illustration of the present invention. However, many other variations of the process, and combinations of the features of the inventive process, are conceivable by the person skilled in the art, without exceeding the scope of the patent claims.

EXAMPLES

TPO plaques based on polyolefin-based thermoplastic elastomer (polypropylene, AW161C, “reactor grade” TPO from Sumitomo Chemical Industries Co., Ltd.)

Example 1 Preparation of the Inventive Mixtures

1a) 100 g of poly-{3-(eicosyltetracosyl)-1-[2,2,6,6-tetramethylpiperidin-4-yl]-pyrrolidine-2,5-dione} (CAS No. 152261-33-1; HALS Ia) were melted by heating and 50 g of hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate (IIIa) were admixed. After homogenization, pastilles were molded from the hot mixture and solidified on cooling. 1b) 40 g of N,N′-bisformyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexa-methylenediamine (IIa) and 20 g of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate were intimately combined in a tumbling mixer.

Example 2 Synergistic Action of the Mixture in Comparison with the Individual Components

Beige-colored TPO plaques with various stabilizers were produced and then weathered to SAE J 1885. The color change (ΔE) was measured after 450 MJ/m² of irradiation. The tables below give the results (where a smaller color change indicates better results):

Stabilizer system ΔE after 450 MJ/m² 1  0.15% of HALS Ia 5.3 2  0.1% of HALS Ia 4.4  0.05% benzoate IIIb 1 0.075% of HALS Ia 3.9 0.075% of HALS IIa 2  0.05% of HALS Ia 0.2  0.05% of HALS IIa  0.05% of benzoate IIIa

It can be seen that the inventive mixtures (in each case No. 2) exhibit better results than the corresponding comparative examples (in each case No. 1) using (mixtures of) HALS compounds.

Example 3 Retention of Gloss on Colored TPO Plaques

Beige-colored TPO plaques with various stabilizers were produced and then weathered to SAE J 1885. Retention of gloss (at an angle of 60°) was measured after 150 and 300 MJ/m² of irradiation. Gloss is a measure of the smoothness of the surfaces. When the surface is degraded it becomes rough, and the gloss values falls. The tables below give the results:

Gloss Gloss (60°) (60°), Gloss (60°) after Stabilizer system reference after 150 MJ/m² 300 MJ/m² 1  0.1% of HALS Ia 72.2 51.8 4.8 0.05% of benzoate IIIb 2  0.1% of HALS IIa 69.5 62.7 55.2 0.05% of benzoate IIIb 3 0.05% of HALS Ia 73.9 57.6 48.8 0.05% of HALS IIa 0.05% of benzoate IIIb 4  0.1% of HALS IV* 70.4 13.0 2.3 0.05% of benzoate IIIb 5  0.1% of HALS V* 71.7 7.1 2.3 0.05% of benzoate IIIb *HALS IV is poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) (CAS No. 71878-19-8, Chimassorb 944); HALS V is N,N′″-[1,2-ethanediylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin- 2-yl]imino]-3,1-propanediyl]]bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,3,5-triazine-2,4,6-triamine (CAS-No. 106990-43-6, Chimassorb 199)

The present results clearly show that the inventive mixtures of HALS and benzoate (Nos. 1-3) exhibit good stabilizing action when comparison is made with the comparative examples using HALS IV (No. 4) and HALS V (No. 5). 

1: A mixture, comprising at least one of (a) and (b), and further comprising (c) and (d): (a) an oligomeric compound, comprising a repeat unit of general formula (I) or an acid-addition salt thereof

in which R¹ is H, C1-C30-alkyl, C2-C22-alkenyl, C1-C20-alkoxy, cyanomethyl, 2-hydroxyethyl, formyl, C₂-C₆-alkanoyl, benzyl, or a moiety of formula —CR⁷═CH—CO—OR⁸, R² is H, C₁-C₃₀-alkyl, or a mixture comprising a C₁₄-C₂₈-alkyl group, R³, R⁴, R⁵, and R⁶, independently of one another, are identical or different C₁-C₃₀-alkyl, R⁷ is H, C₁-C₆-alkyl, or a moiety of formula CO—OR⁸, R⁸ is C₁-C₁₈-alkyl, C₃-C₁₅-cycloakyl, C₇-C₁₈-aralkyl, phenyl or tolyl, (b) a compound of general formula (II) or an acid-addition salt thereof

in which n is 1 or 2, R⁹ is H or C₁-C₄-alkyl, R¹⁰, R¹¹, R¹², and R¹³, independently of one another, are identical or different C₁-C₄-alkyl, or R¹⁰ and R¹¹ or R¹² and R¹³ together are a tetramethylene group or pentamethylene group, R¹⁴ is H, C₁-C₃₀-alkyl, or C₂-C₂₂-alkenyl, or unsubstituted or C₁-C₄-alkyl-, halogen-, C₁-C₄-alkoxy-, methylenedioxy-, ethylenedioxy-, and/or di-C₁-C₄-alkylamino-substituted C₇-C₁₂-phenylalkyl, C₁-C₂₂-alkanoyl, C₂-C₃-cyanoalkyl, C₁-C₂₂-hydroxyalkyl or C₂-C₂₂-aminoalkyl, R¹⁶ is H or C₁-C₃₀-alkyl, and if n=1 R¹⁵ is H, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl, C₃-C₁₂-cycloalkyl or bicycloalkyl, or cyano-, hydroxyl-, or carbo-C₁-C₄-alkoxy-substituted C₂-C₂₂-alkyl, or ether-oxygen-, nitrogen-, or sulfur-interrupted C₄-C₂₂-alkyl, or unsubstituted or C₁-C₄-alkyl-, halogen-, C₁-C₄-alkoxy-, methylenedioxy-, ethylenedioxy-, or di-C₁-C₄-alkylamino-substituted C₇-C₂₂-phenyl- or diphenylalkyl, or unsubstituted or C₁-C₄-alkyl- or carbo-C₁-C₄-alkoxy-substituted phenyl, or a moiety of general formula (IV)

or C₁-C₂₂-alkyl comprising heterocyclic moieties, and, if n=2, R¹⁵ is C₂-C₂₂-alkylene, C₅-C₂₂-cycloalkylene, C₈-C₁₄-phenylalkylene, or phenylene, or ether-oxygen-, nitrogen-, or sulfur-interrupted C₄-C₃₀-alkylene, or C₄-C₃₀-alkylene interrupted by 5- or 6-membered heterocyclic moieties, (c) at least one compound of general formula (III)

in which R¹⁷ is C₁-C₂₀-alkyl or aryl, and (d) optionally further additives, wherein each of the substituents R¹ to R¹⁷ has interruption at any desired position by one or more heteroatoms, where the number of the heteroatoms is not more than 10, and optionally each of the substituents R¹ to R¹⁷ has substitution at any desired position, but not more than five times, by C₁-C₃₀-alkyl, C₁-C₂₀-alkoxy, aryl, heterocyclic moieties, heteroatoms, or halogen, and the likewise has substitution at most twice, by the substituents or by substituted aryl moieties. 2: The mixture according to claim 1, wherein (d) is present and comprises an antioxidant. 3: The mixture according to claim 1, wherein R² is a mixture comprising C₁₄-C₂₈-alkyl groups, where two of the alkyl groups which are not permitted to differ from one another by more than two carbon atoms make up respectively at least 30% of the mixture. 4: The mixture according to claim 1, wherein component (a) comprises an oligomeric compound having a repeat unit of the general formula (I), wherein R³, R⁴, R⁵ and R⁶═CH₃ and R²═C₁₆-C₂₆-alkyl. 5: The mixture according to claim 1, wherein component (a) comprises a compound of the general formula (I), wherein R³, R⁴, R⁵ and R⁶ are methyl, and R² is a hydrogen atom or C₂-C₁₀-alkyl. 6: The mixture according to claim 1, wherein component (c) comprises a compound of the general formula (III), where R¹⁷═C₁₆-alkyl. 7: The mixture according to claim 1, wherein component (c) comprises a compound of the general formula (III), where R¹⁷=2,4-di-tert-butylphenyl. 8: The mixture according to claim 1, where a ratio by weight of at least one of components (a) and (b) to component (c) is from 10:1 to 1:2. 9: The mixture according to claim 1, wherein the mixture is capable of stabilizing a non-living organic material with respect to exposure to at least one of light, oxygen, and heat. 10: The mixture according to claim 9, wherein the non-living organic material comprises at least one polymer selected from the group consisting of thermoplastic elastomers, polyolefins, polystyrene, copolymers of styrene or of α-methylstyrene, polyesters, polycarbonates, polyvinyl chloride, polyacrylates, polymethacrylates, polyurethanes, and physical blends thereof. 11: The mixture according to claim 10, the non-living organic material is an olefin-based thermoplastic elastomer. 12: A non-living organic material, comprising at least one mixture according to claim
 1. 13: An article, produced from the non-living organic material according to claim
 12. 14: A process for stabilizing a non-living organic material with respect to exposure to at least one of light, oxygen, and heat, comprising adding an effective amount of at least one mixture according to claim 1 to the non-living organic material. 15: The mixture according to claim 1, wherein component (a) is present. 16: The mixture according to claim 1, wherein component (b) is present. 17: The mixture according to claim 1, wherein component (a) and component (b) are present. 18: The mixture according to claim 15, wherein R¹ is C₁-C₆-alkoxy. 19: The mixture according to claim 16, wherein R¹⁴ is formyl, acyl or benzyl. 